Stable solid formulations of cyclohexenone oxime ether herbicides

ABSTRACT

Crop protection active compound formulations, comprising a cyclohexenone oxime ether of the general formula I ##STR1## where the radicals R 1  -R 6  have the following meanings: R 1  is ethyl or propyl; 
     R 2  is hydrogen or an equivalent of an agriculturally utilizable cation; 
     R 3  is 2-thioethylpropyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1-methylthiocyclopropyl, 5-isopropylisoxazol-3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl; 
     R 4  and R 5  independently of one another are hydrogen, methyl or methoxycarbonyl; 
     Alk is CH 2  CH 2 , CH 2  CH(CH 3 ), CH 2  CH═CH, CH 2  CH═C(Cl) or CH 2  CH 2  CH═CH; 
     R 6  is hydrogen, phenyl, halophenyl, dihalophenyl, phenoxy, halophenoxy or dihalophenoxy; 
     and a water-soluble basic salt of an acid having a pK a  of greater than 5, alkali metal hydroxides and alkali metal carbonates being excluded, their preparation and use as herbicides are described.

This application is a 371 of pct/EP96/01046 filed Mar. 3, 1996.

The present invention relates to crop protection active compoundformulations, comprising a cyclohexenone oxime ether of the generalformula I ##STR2## where the radicals R¹ -R⁶ have the followingmeanings: R¹ is ethyl or propyl;

R² is hydrogen or an equivalent of an agriculturally utilizable cation;

R³ is 2-thioethylpropyl, tetrahydrothiopyran-3-yl,tetrahydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl,1-methylthiocyclopropyl, 5-isopropylisoxazol-3-yl,2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or2,4,6-trimethyl-3-butyrylphenyl;

R⁴ and R⁵ independently of one another are hydrogen, methyl ormethoxycarbonyl;

Alk is CH₂ CH₂, CH₂ CH(CH₃), CH₂ CH═CH, CH₂ CH═C(Cl) or CH₂ CH₂ CH═CH;

R⁶ is hydrogen, phenyl, halophenyl, dihalophenyl, phenoxy, halophenoxyor dihalophenoxy;

and a water-soluble basic salt of an acid having a pK_(a) of greaterthan 5, and their preparation and use as herbicides.

Cyclohexenone oxime ethers of the general formula I have been known asherbicides for a long time. Moreover, in small amounts they act asgrowth regulators.

The herbicidally active cyclohexenone oxime ethers of the generalformula I are disclosed, inter alia, in DE-A 24 39 104, DE-A 28 22 304,DE-A 38 08 072, DE-A 38 38 309, EP-A 046 860, EP-A 066 195, EP-A 071707, EP-A 088 299, EP-A 088 301, EP-A 115 808, EP-A 125 094, EP-A 137174, EP-A 142 741, EP-A 177 913, EP-A 228 598, EP-A 230 235, EP-A 230260, EP-A 238 021, EP-A 243 313, EP-A 254 514, EP-A 319 835, EP-A 456068, EP-A 456 069, EP-A 456 112, EP-A 456 118,

U.S. Pat. No. 4,440,566, JP-A 54/191 945 and Proceedings Brit. CropProtection Conference--Weeds 1985, Vol. 1, pages 93-98.

Metal salts of cyclohexenone oxime ethers are also disclosed, interalia, in the earlier German Patent Application having the file reference195 45 212.7.

These compounds are in general used in the form of water-dispersiblepowders (WP) or water-dispersible granules (WG), and also asemulsifiable concentrates (EC). Some compounds of this class ofsubstances are marketed as water-soluble formulations in which theactive compound is present as the alkali metal salt. A disadvantage ofthe emulsifiable concentrates is that, beside the actual activecompound, large amounts of organic solvents are also applied during use.It has additionally been shown that the active compounds are unstable inorganic solvents in the presence of emulsifiers or of water present intraces and decompose (cf., for example, EP-A 394 847 and EP-A 266 068).

Water-dispersible solid formulations (WP or WG) do avoid the use oforganic solvents, but require a higher expenditure on preparation of theformulation. The often low-melting or liquid active compounds must beabsorbed on carrier material in order to be accessible to the necessaryfine grinding. The addition of auxiliaries and carriers additionallyleads to the fact that the active compound contents in the formulationshave to precipitate to a low extent, which leads to increased packagingand transportation costs. Examples of such formulations are found, interalia, in EP-A 488 645.

Water-soluble formulations have also been described previously. It isalso seen here that the chemical instability of the cyclohexenone oximeethers stands in the way of a practical solution. A lithium salt, forexample, is thus described in JP 62089 635.

The preparation of various salts, among these salts of transitionmetals, by double decomposition is described in various applications. Inpractice, this process appears unsuitable as in the end sufficientstability is not achieved. (JP 59 1633 63, JP 8144 384, U.S. Pat. No.4,741,768, DE 3941160).

The preferred manner of preparation of alkali metal salts is theextraction of the active compounds from organic solution using anaqueous solution of the alkali metal hydroxides (eg. DE 3941160).

It is an object of the present invention to develop storage-stable solidformulations of cyclohexenone oxime ethers of the general formula I anda process for their preparation.

We have found that this object is surprisingly achieved by the cropprotection active compound formulation described at the out-set.

Within the meaning of the present invention, the cyclohexenone oximeethers are weak organic acids having pK_(a) s between 4 and 5. Their lowsolubility in water in the neutral range distinctly increases at basicpHs. It is thus possible by suitable combination of cyclohexenones withbasic water-soluble substances (acid acceptors) to obtain water-solublemixtures.

Beside the alkali metal hydroxides and alkali metal carbonates mentionedin the literature, basic water-soluble substances which are suitable forthis purpose are those which are to be interpreted as alkali metal saltsof those acids whose pK_(a) is greater than 5. The pK_(a) of theparticular cyclohexenone is preferably checked and then a basicsubstance is selected whose underlying pK_(a) is greater than that ofthe cyclohexenone in question.

It is to be expected that the following reaction commences in thepresence of water: ##STR3##

A requirement for a clear solution then being formed is also that theconjugate acid HX formed is also water-soluble.

Beside water-solubility, the formulations of cyclohexenone andwater-soluble basic salt (acid acceptor) according to the invention havea distinctly improved storage stability at elevated temperatures than,for example, the free active compounds or their alkali metal salts whichwere obtained from the cyclohexenones with alkali metal hydroxides oralkali metal carbonates.

Adequate storage stability is an essential feature of commerciallymarketable and registrable crop protection agents. Decreaseddecomposition of the active compound per se is also an economicadvantage.

Suitable water-soluble basic salts for achieving the described watersolubility and storage stability of the active compound are:metaborates, phosphates, hydrogen phosphates, pyrophosphates,metasilicates, orthosilicates, tetraborates, sulfites,tripolyphosphates, polyphosphates, metaphosphates, citrates, tetrasodiumEDTA, trisodium nitrilotriacetate, guanidine acetate, guanidinecarbonate, and mixtures of these.

The following basic water-soluble salts are preferred: ammonium andalkali metal metaborates, tetraborates, metasilicates, orthosilicates,phosphates, hydrogen phosphates, pyrophosphates, tripolyphosphates,polyphosphates, sulfites, citrates, tetrasodium EDTA, trisodiumnitrilotriacetic acid, guanidine carbonate and guanidine acetate. Thesalts can be employed in anhydrous form and in the form of theirhydrates.

Alkali metal metaborates, alkali metal tetraborates, alkali metal andammonium metasilicates, trialkali metal and triammonium phosphates,alkali metal and ammonium hydrogen phosphates, alkali metalpyrophosphates, alkali metal tripolyphosphates, alkali metal sulfites,alkali metal citrates, tetrasodium EDTA, trisodium nitrilotriaceticacid, guanidine carbonate and guanidine acetate are particularlypreferred, it being possible for the salts to be present in anhydrousform or as hydrates.

The sodium and potassium salts are preferred.

Tetrasodium pyrophosphate, dipotassium hydrogen phosphate, guanidinecarbonate, tetrasodium EDTA, trisodium nitrilotriacetic acid andespecially sodium metaborate, sodium metasilicate and trisodiumphosphate have proven to be very particularly suitable from which, inturn, sodium metasilicate particularly stands out.

Preferred cyclohexenone herbicides are:

2-(N-ethoxybutyrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one(sethoxydim),

2-(1-allyloxyiminobutyl)-4-methoxycarbonyl-5,5-dimethyl-3-oxocyclohexenol(alloxydim),

2-(N-ethoxybutyrimidoyl)-5-(2-phenylthiopropyl)-3-hydroxy-2-cyclohexen-1-one,

5-(2,4,6-trimethylphenyl)-3-hydroxy-2-[1-(ethoxyimimo)propyl]-cyclohex-2-en-1-one(tralkoxydim),

2-(N-ethoxybutyrimidoyl)-3-hydroxy-5-(tetrahydropyran-3-yl)cyclo-hexen-1-one,

1-[1-ethoxyiminobutyl]-3-hydroxy-5-(tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one(cycloxydim),

2-[1-[(E)-3-chloroallyloxy]iminopropyl]-5-(2-ethylthiopropyl)-3-hydroxycyclohex-2-enone(clethodim),

2-(1-(3-chloroallyloxyiminobutyl)-5-(2-ethylthio)propyl)-3-hydroxycyclohex-2-enone(cloproxydim),

2-(1-(3-chloroallyloxy)iminopropyl)-5-(1,3-dimethylpyrazol-5-yl)-3-hydroxycyclohex-2-enone,

2-(1-(3-chloroallyloxy)iminopropyl)-5-(1-thiomethylcyclopropyl)-3-hydroxycyclohex-2-enone,

2-(1-ethoxyiminopropyl)-5-(2,4,6-trimethyl-3-butyrylphenyl)-3-hydroxycyclohex-2-enone(butroxydim),

2-(1-(3-chloroallyloxy)iminopropyl)-5-(tetrahydropyran-4-yl)-3-hydroxycyclohex-2-enone,

2-(1-(2-p-chlorophenoxypropyloxy)iminobutyl-5-(tetrahydrothio-pyran-3-yl)-3-hydroxycyclohex-2-enoneor mixtures thereof.

Particularly preferred cyclohexenone herbicides are:

sethoxydim, cycloxydim, clethodim, tralkoxydim, butroxydim,2-(1-(3-chloroallyloxy)iminopropyl)-5-(tetrahydropyran-4-yl)-3-hydroxycyclohex-2-enone,2-(1-(2-p-chlorophenoxypropyloxy)-iminobutyl-5-(tetrahydrothiopyran-3-yl)-3-hydroxy-cyclohex-2-en-oneor mixtures thereof.

The cyclohexenone oxime ethers of the general formula I can be obtainedduring preparation as isomer mixtures, both E/Z isomer mixtures andenantiomer or diastereoisomer mixtures being possible. If desirable, theisomer mixtures can be separated by the methods customary for thispurpose, eg. by chromatography or by crystallization.

The cyclohexenone oxime ethers of the general formula I can be presentin several tautomeric forms, which are all covered by the invention.

The invention comprises solid water-soluble formulations, preferably inthe form of powders or granules, which as the herbicidal componentcomprise a cyclohexenone oxime ether and a water-soluble basic salt. Theproportion of the cyclohexenone oxime ether is from 5 to 95%, preferablyfrom 10 to 85%, and the proportion of the basic salt is from 5 to 95%,preferably from 15 to 90%, based on the sum of cyclohexenone oxime etherand basic salt.

In order to guarantee use in accordance with practice, it may benecessary to add further formulation auxiliaries. These include, forexample, herbicidally active compounds, antidotes, water-soluble salts,dispersants, wetting agents, binders, lubricants, absorptive carriers,antifoams, preservatives, colorants, pigments or further adjuvants orsurfactants customary in agricultural practice.

Additional water-soluble salts can be: sodium chloride, potassiumchloride, ammonium sulfate, sodium sulfate, potassium sulfate, potassiumcarbonate and sodium carbonate.

Further herbicidally active compounds can be:

2,4-D, 2,4-DB, acetochlor, acifluorfen, aclonifen, alachlor,allidochlor, ametryn, amidosulfuron, amitrole, anilofos, asulam,atrazine, azimsulfuron, aziprotryne, barban, benazolin, benfluralin,benfuresate, bensulfuron, bensulide, bentazone, benzofenap, benzofluor,benzoylprop, benzthiazuron, bifenox, bisalafos, bromacil, bromobutide,bromofenoxim, bromoxynil, buminafos, butachlor, butamifos, butenachlor,buthidazole, butralin, buturon, butylate, cafenstrole, carbetamide,chloramben, chlorbromuron, chlorbufam, chlorfenac, chloridazon,chlorimuron, chlornitrofen, chlorfenprop, chloroxuron, chlorpropham,chlorsulfuron, chlorthal-dimethyl, chlorthiamid, chlortoluron,cinmethylin, cinosulfuron, clodinafop, clomazone, clomeprop, clopyralid,cumyluron, cyanazine, cycloate, cyclosulfamuron, cycluron, cyhalofop,cyperquat, cyprazine, cyprazole, dalapon, desmedipham, desmetryn,di-allate, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop,diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron,dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoseb,dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diuron, DNOC,dymron, eglinazine, endothal, EPTC, esprocarb, ethalfluralin,ethametsulfuron, ethidimuron, ethiozin, ethofumesate, ethoxyfen,etobenzanid, fenoprop, fenoxaprop, fenoxaprop-P, fenthiaprop, fenuron,flamprop, flazasulfuron, fluazifop, fluazifop-P, fluchloralin,flumetsulam, flumiclorac, flumioxazin, flumipropyn, fluometuron,fluorbentranil, fluorochloridone, fluorodifen, fluoroglycofen, flupoxam,flupropacil, fluridone, fluroxypyr, flurtamone, fomesafen, fosamine,furyloxyfen, glufosinate-ammonium, glyphosate, halosulfuron, haloxyfop,haloxyfop-P, hexazinone, imazamethapyr, imazapyr, imazaquin,imazethabenz, imazethapyr, imazosulfuron, ioxynil, isocarbamid,isopropalin, isoproturon, isouron, isoxaben, isoxapyrifop, karbutilate,lactofen, lenacil, linuron, maleic hydrazide, MCPA, MCPB, mecoprop,mecoprop-P, mefenacet, mefluidide, metamitron, metazachlor,methabenzthiazuron, methazole, metobenzuron, metolachlor, metosulam,metoxuron, metribuzin, metsulfuron, minoterb, molinate, monalide,monolinuron, monuron, napropamide, naproanilide, naptalam, NCC 330,neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxyfluorfen,paraquat, pebulate, pendimethalin, perfluidone, phenisopham,phenmedipham, picloram, piperophos, PPG-1013, pretilachlor,primisulfuron, procyazine, prodiamine, profluralin, prometon, prometryn,propyzamide, propachlor, propanil, propaquizafop, propazine, propham,prosulfocarb, prosulfuron, prynachlor, pyrazolate, pyrazosulfuron,pyrazoxyfen, pyributicarb, pyridate, pyrithiobac, quinclorac, quinmerac,quizalofop, quizalofop-P, rimsulfuron, secbumeton, siduron, simazine,simetryn, sulcotrione, sulfallate, sulfentrazone, sulfometuron-methyl,sulfosate, tebuthiuron, terbacil, terbucarb, terbuchlor, terbumeton,terbuthylazine, terbutryn, thiazopyr, thidiazimin,thifensulfuron-methyl, thiobencarb, tiocarbazil, triallate,triasulfuron, triazofenamid, tribenuron, triclopyr, tridiphane,trietazine, trifluralin, triflusulfuron, trimeturon, vernolate,xylachlor or mixtures of these. The co-herbicides can be water-solubleor water-insoluble.

In the case of water-insoluble compounds, these are present as finelyground powders. It is additionally possible to introduce these into theformulation in the form of water-dispersible granules. In the case ofwater-soluble co-herbicides, these can be present in the form of thefree acid or as its salt.

Dispersants or wetting agents which can be used, inter alia, are:alkylarylsulfonates; phenylsulfonates; alkylsulfates; alkylsulfonates;alkyl ether sulfates; alkyl aryl ether sulfates; alkyl polyglycol etherphosphates; polyarylphenyl ether phosphates; alkylsulfosuccinates;olefinsulfonates; paraffinsulfonates; petroleumsulfonates; taurides;sarcosides; fatty acids; alkylnaphthalenesulfonic acids;naphthalenesulfonic acids; lignosulfonic acids; condensation products ofsulfonated naphthalenes with formaldehyde; or with formaldehyde andphenol; ligninsulfite waste liquor; including their alkali metal,alkaline earth metal, ammonium and amine salts; alkylphenol alkoxylates;alcohol alkoxylates; fatty amine alkoxylates; polyoxyethylene glycerolfatty acid esters; castor oil alkoxylates; fatty acid alkoxylates; fattyacid amide alkoxylates; fatty acid polydiethanolamides; lanolinethoxylates; EO/PO block copolymers; fatty acid polyglycol esters;isotridecyl alcohol; fatty acid amides; methylcellulose; fatty acidesters; silicone oils; alkyl polyglycosides; glycerol fatty acid esters;alkyl phosphates; quaternary ammonium compounds, amine oxides; betainesand mixtures of these. The dispersants and wetting agents are knownsubstances and are described in greater detail, for example, in:McCutcheons: Emulsifiers & Detergents, MC Division, Glen Rock N.J.;Stache, Tensid Taschenbuch [Surfactant Handbook], Hanser Verlag.

Binders which can be used are:

polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, starch,vinylpyrrolidone/vinyl acetate copolymers and mixtures thereof.

Lubricants which can be used are: Mg stearate, Na stearate, talc,polyethylene glycol and mixtures thereof.

Absorptive carrier materials which can be used are: mineral earths suchas silicic acids, silica gels, silicates, talc, kaolin, attaclay,limestone, chalk, bole, loess, clay, dolomite, diatomaceous earth,calcium sulfate and magnesium sulfate, magnesium oxide, ground syntheticmaterials, fertilizers such as ammonium sulfate, ammonium phosphate,ammonium nitrate and ureas, vegetable products such as grain flour, treebark meal, wood meal and nutshell meal, cellulose powder, attapulgite,montmorillonite, mica, vermiculite, synthetic silicic acids, syntheticcalcium silcates and mixtures thereof.

Suitable antifoams are, for example, silicone emulsions, long-chainalcohols, fatty acids, organofluorine compounds and mixtures thereof.

The formulation auxiliaries can be additionally used in the cropprotection active compound formulation in a concentration from 0 to 95%by weight. If they are a constituent of the formulation, from 5 to 95%by weight have proven suitable.

Further crop protection active compounds can be additionally used in aconcentration from 0 to 90% by weight. If they are a constituent of theformulation, from 10 to 90% by weight have proven suitable. The % byweight mentioned relate to the total weight of the crop protectionactive compound formulation.

The solid formulations according to the invention can be prepared invarious manners known in principle to the person skilled in the art.

Suitable formulations are powders, granules, briquets, tablets andsimilar solid formulations. In addition to powders, granules areparticularly preferred. The powders can be water-soluble orwater-dispersible powders. The granules can be water-soluble orwater-dispersible granules for use in spray application or broad-castinggranules for direct application. The average particle size of thegranules is from 200 μm to 2 mm.

Since these formulations are often hygroscopic substances, or for thepurpose of preventive user protection, for instance, the formulationscan be packaged in water-soluble film bags. Preferably, a watervapor-impermeable outer covering such as polyethylene film,polyethylene-laminated paper or aluminum foil is additionally employedin the packaging.

Suitable water-soluble films consist of the following materials:

polyvinyl alcohol, cellulose derivatives such as methylcellulose orcarboxymethylcellulose.

Undesired vegetation is controlled by allowing a herbicidally activeamount of a crop protection active compound formulation to act on thecrop plant, its habitat and/or on its seed.

The following preparation processes are suitable for the formulationsaccording to the invention:

a) Active Compound is Solid

1) Mixing of active compound, basic salt and further auxiliaries,commutation if desired and subsequent agglomeration.

The processes of extruder granulation, disk granulation, fluidized bedgranulation or mixer granulation, for example, are suitable foragglomeration. If appropriate, the granules obtained are then dried.

2) Mixing of active compound, basic salt and further auxiliaries,commutation if desired and subsequent compaction.

b) Active Compound is an Oil or a Solid

1) Extraction of the cyclohexenone oxime ether dissolved in an organicsolvent by means of an aqueous solution of the basic salt in the aqueousphase and subsequent removal of the water.

Suitable organic solvents are water-immiscible, or only partiallymiscible, solvents such as hydrocarbons, aromatic hydrocarbons,halogenated aliphatic or aromatic hydrocarbons, ethers, carboxylic acidesters, carboxamides, ketones and alcohols.

Spray drying, vacuum drying, fluidized bed drying and freeze drying, forexample, are suitable for evaporating the water.

The solids obtained in this way can then be additionally processed asunder a).

The aqueous solution thus obtained can furthermore be applied to anabsorptive carrier material, e. g. by spraying or mixing. Broadcastinggranules, for example, can be obtained in this manner.

FORMULATION EXAMPLES

a) Test Methods

The active compound content of the formulations was in each casedetermined by means of quantitative HPLC, and is indicated in percent.

Experiments on shelf life

To investigate the shelf life, samples of the particular formulationwere stored for a specific time at the particular temperature indicatedin tightly closed glass vessels. The samples were then examined andcompared with the comparison value at the start of storage (zero value).The active compound content is indicated as the relative proportion,based on the zero value (in percent).

Experiments on dissolution behavior

2 g of the formulation were added in one portion to 100 ml of CIPACstandard water D which was stirred at about 100 rpm by means of amagnetic stirrer. The time which passed until the entire solid producthad disintegrated or dissolved was taken.

b) Formulation Experiments

The following compounds were used for formulation experiments:

Compound A: sethoxydim

Compound B: cycloxydim

Compound C:2-(1-(3-chioroallyloxy)imino-propyl)-5-(tetrahydropyran-4-yl)-3-hydroxycyclohex-2-enone

Compound D:2-(1-(2-p-chlorophenoxypropyloxy)imino-butyl-5-(tetrahydrothiopyran-3-yl)-3-hydroxycyclohexenone

Comparison Example 1

51.4 g of compound C (content 97%) were mixed with a mixture of 1 partof sodium carbonate and 1 part of sodium hydrogen carbonate (48.6 g) for60 sec in an IKA laboratory mill (type M 20). The mixture was soluble inwater within less than 5 min. The active compound content was 49.3%.

Example 1

51.4 g of compound C (content 97%) were mixed with sodium metasilicate(48.6 g) for 60 sec in an IKA laboratory mill (type M 20). The mixturewas soluble to give a clear solution in water within less than 5 min.The active compound content was 42%.

Example 2

51.4 g of compound C and 48.6 g of trisodium phosphate dodecahydratewere mixed as described in Ex. 1. Active compound content: 46%.

The storage stability at room temperature was observed for 3 months andcompared.

    ______________________________________                                                      Relative content of compound C after                                            1 month [%]                                                                             3 months [%]                                        ______________________________________                                        Comparison Example 1                                                                          91        68                                                    Example 1 100 95                                                              Example 2 99 78                                                             ______________________________________                                    

Comparison Example 2

500 g of active compound C were dissolved in 1,000 g of toluene. Thissolution was mixed with a solution of 58.5 g of sodium hydroxide in 650g of water for 1 hour. After phase separation, the homogeneous aqueousphase was separated off and then dried to give granules in a laboratoryfluidized bed granulator at an inlet temperature of the drying air of120° C. The active compound content was 86.8%. The granules dissolvedrapidly and completely on introducing into water.

Comparison Example 3

92.3 g of active compound D were dissolved in 90 g of toluene. Thissolution was mixed with a solution of 7.66 g of sodium hydroxidesolution in 100 g of water for 1 hour. After phase separation, thehomogeneous aqueous phase was separated off, washed with MTB ether andthen dried to give a solid product in a vacuum drying oven at a dryingtemperature of 40° C. The solid product had an active compound contentof 87.1% and dissolved rapidly and completely on introducing into water.

Comparison Example 4

A 30% strength solution of active compound D in toluene was extractedwith 2.5% strength NaOH. The aqueous phases were collected and dried at70° C. in a vacuum drying oven. The solid obtained had an activecompound content of 84.6% and was soluble in water to give a clearsolution within 2 min.

Example 3

50 ml of a 50% strength solution of compound A in tert-butyl methylether were shaken with a solution of 10.2 g of sodium 35 metasilicate in50 ml of water. After separating off the aqueous phase, the ether phasewas washed with 30 ml of water. The combined aqueous phases wereevaporated in vacuo at 70° C. The solid residue obtained was soluble togive a clear solution in water within 2 min. Active compound content:70%.

Example 4

50 ml of a solution of cycloxydim (compound B) in Solvesso 150 (430 g/l)were extracted with a solution of 17.7 g of sodium metasilicate in 85 mlof water. After separating off the aqueous phase, the organic phase waswashed with 30 ml of water and the combined aqueous phases wereevaporated in vacuo at 70° C. The residue obtained was soluble in waterto give a clear solution within 2 min. Active compound content: 57%.

Example 5

A mixture of sodium metaborate hydrate (48.6 g) and compound C (51.4 g)was first mixed in an IKA universal mill, type M 20, and then treatedsuccessively with 7.2 ml of water. The material thus obtained wasextruded using a basket extruder bench apparatus (Fitzpatrick CompanyEurope, type KAR 75) with a screen size of 0.8 mm. The granules obtainedwere dried at 60° C. Active compound content: 55%. The granulesdissolved completely in water in less than 4 min.

Example 6

A mixture of sodium phosphate dodecahydrate (58.9 g) and compound C(41.1 g) was extruded as described in Example 5 with addition of 3.8 mlof water. Active compound content: 52%. The granules dissolved in waterto give a clear solution within 3 min.

Example 7

A mixture of sodium metasilicate (48.6 g) and compound C (51.4 g) wasextruded as described in Example 5 with addition of 25 g of water.Active compound content: 45%. The granules dissolved in water to give aclear solution within 2 min.

Example 8

A mixture of compound C (72%) and sodium metasilicate (28%) was mixed inan IKA type M 20 universal mill and made into a paste with addition of atotal of 22.5 g of water. The material obtained was extruded asdescribed in Example 5 and the granules obtained were dried at 60° C.Active compound content: 64%. The granules dissolved in water to give aclear solution within 2 min.

Example 9

217.5 g of active compound C were dissolved in 200 g of toluene. Thissolution was mixed with a solution of 82.5 g of sodium metasilicate in300 g of water for 1 hour. After phase separation in a separatingfunnel, the homogeneous aqueous phase was separated off and then driedto give granules in a laboratory fluidized bed granulator (Combi Coater,Niro Aeromatic) at an inlet temperature of the drying air of 120° C.

The active compound content was 64.2%. The granules dissolved rapidlyand completely on introducing into water.

Example 10

16.0 g of sodium metasilicate and 84.82 g of active compound C weremixed and reacted in 100 g of water. An aqueous solution was formed.This was dried in a vacuum drying oven at a drying temperature of 70° C.to give a solid product. The active compound content was 73.7%. Thesolid product dissolved rapidly and completely on introducing intowater.

Example 11

79.8 g of active compound D were dissolved in 100 g of toluene. Thissolution was mixed and reacted with a solution of 20.8 g of sodiummetasilicate in 100 g of water for 1 hour. After allowing to stand, 3phases were formed. The two lower, aqueous phases were separated off ina separating funnel and then dried at a drying temperature of 70° C. ina vacuum drying oven to give a solid product having an active compoundcontent of 78.7%. The solid product dissolved rapidly and completely onintroducing into water.

Example 12

88.75 g of active compound D were dissolved in 100 g of toluene. Thissolution was mixed and reacted with a solution of 11.6 g of sodiummetasilicate in 100 g of water for 1 hour. After allowing to stand, 3phases were formed. The two lower, aqueous phases were separated off ina separating funnel and then dried at a drying temperature of 70° C. ina vacuum drying oven to give a solid product having an active compoundcontent of 88.4%. The solid product dissolved rapidly and completely onintroducing into water.

Example 13

Compound C (7.6 g) and bentazone sodium salt (84.7 g; content about 85%)were intimately mixed together with sodium metasilicate (7.7 g) in anIKA universal mill and then moistened with 8.5 ml of water. Afterextrusion of the material obtained, granules which were soluble in waterto give a clear solution within 1 min were obtained. Active compoundcontent (compound C): 45 6.8%.

Example 14

84.7 g of Na bentazone, 7.6 g of compound C, 7.7 g of sodium metaborateand 6 ml of water were mixed and extruded as described in Example 13.The granules obtained were soluble in water to give a clear solutionwithin 1 min.

Active compound content (compound C): 6.5%.

Table: Results of the experiments on shelf life of active compounds informulations at specific temperatures and at a storage time of 30 days.The relative active compound content (%) based on the initial content isindicated.

    ______________________________________                                                     20° C.                                                                       30° C.                                                                          40° C.                                                                         50° C.                             ______________________________________                                        Comparison Example No.                                                          2 100 99 88 42                                                                3 100 98 88 40                                                                4 100 96 80 19                                                                Example No.                                                                   4 100 100 96 96                                                               5 100 100 98 83                                                               6 100 99 99 87                                                                7 100 100 100 99                                                              8 100 100 100 100                                                             9 100 100 100 78                                                              10   100 100 99 77                                                            11  99 99 99 85                                                               12  99 99 99 90                                                             ______________________________________                                    

We claim:
 1. A stable, water-soluble crop protection solid activecompound formulation, comprising a cyclohexenone oxime ether of thegeneral formula I ##STR4## where the radicals R¹ -R⁶ have the followingmeanings: R¹ is ethyl or propyl;R² is hydrogen or an equivalent of anagriculturally utilizable cation; R³ is 2-thioethylpropyl,tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl,tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1-methylthiocyclopropyl,5-isopropylisoxa-zol-3-yl, 2,5-dimethylpyrazol-3-yl,2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl; R⁴ and R⁵independently of one another are hydrogen, methyl or methoxycarbonyl;Alk is CH₂ CH₂, CH₂ CH(CH₃), CH₂ CH═CH, CH₂ CH═C(Cl) or CH₂ CH₂ CH═CH;R⁶ is hydrogen, phenyl, halophenyl, dihalophenyl, phenoxy, halophenoxyor dihalophenoxy;and a water-soluble basic salt of an acid having apK_(a) of greater than 5, alkali metal hydroxides, alkali metalcarbonates and where: a said formulation excludes ammonium salts.
 2. Astable, water-soluble crop protection solid active compound formulationas claimed in claim 1, comprising, as crop protection active compound, acyclohexenone oxime ether from the group consisting of sethoxydim,cycloxydim, clethodim, tralkoxydim, butroxydim,2-(1-(3-chloroallyloxy)iminopro-pyl)-5-(tetrahydropyran-4-yl)-3-hydroxycyclohex-2-enone,2-(1-(2-p-chlorophenoxypropyloxy)-iminobutyl-5-(tetrahydrothiopyran-3-yl)-3-hydroxycyclohex-2-enoneor mixtures thereof.
 3. A stable, water-soluble crop protection solidactive compound formulation as claimed in claim 1, comprising aswater-soluble salt a metaborate, phosphate, hydrogen phosphate,pyrophosphate, metasilicate, orthosilicate, tetraborate, sulfite,tripolyphosphate, polyphosphate, metaphosphate, tetrasodium EDTA,trisodium nitrilotriacetate, guanidine acetate, guanidine carbonate ormixtures thereof.
 4. A stable, water-soluble crop protection solidactive compound formulation as claimed in claim 1, comprising aswater-soluble basic salt an alkali metal metaborate, alkali metaltetraborate, alkali metal metasilicate, trialkali metal phosphate,alkali metal hydrogen phosphate, alkali metal pyrophosphate, alkalimetal tripolyphosphate, alkali metal sulfite, alkali metalpolyphosphate, tetrasodium EDTA, trisodium nitrilotriacetate, guanidinecarbonate, guanidine acetate or mixtures thereof.
 5. A stable,water-soluble crop protection solid active compound formulation asclaimed in claim 1, furthermore comprising formulation auxiliaries.
 6. Astable, water-soluble crop protection solid active compound formulationas claimed in claim 1, comprising further crop protection activecompounds.
 7. A stable, water-soluble crop protection solid activecompound formulation as claimed in claim 1, comprisingfrom 5 to 95% byweight of a cyclohexenone oxime ether of the general formula I, from 5to 95% by weight of a water-soluble basic salt, from 0 to 95% by weightof a formulation auxiliary, from 0 to 90% by weight of further cropprotection active compounds.
 8. A process for preparing a cropprotection solid active compound formulation as claimed in claim 1,which comprises mixing a cyclohexenone oxime ether of the generalformula I, the water-soluble basic salt, formulation auxiliaries andoptionally further crop protection active compounds, optionallycomminuting and then agglomerating or compacting.
 9. A process forpreparing a crop protection solid active compound formulation as claimedin claim 1, which comprises dissolving a cyclohexenone oxime ether ofthe general formula I in an organic solvent, extracting with an aqueoussolution of the water-soluble basic salt and then removing the water.10. A process as claimed in claim 9, wherein the crop protection solidactive compound formulation is optionally comminuted after removing thewater and then agglomerated or compacted.
 11. A process as claimed inclaim 8, wherein extruder granulation, disk granulation, fluidized bedgranulation or mixer granulation is used for agglomeration.
 12. Aprocess for controlling undesired vegetation, which comprises dissolvinga herbicidally active amount of a crop protection solid active compoundformulation as claimed in claim 1 and applying the active compound tothe crop plant, its habitat and/or on its seed.
 13. A stable,water-soluble crop protecion solid active compound formulation asdefined in claim 1, comprising, as crop protection active compound, acyclohexenone oxime ether I whereinR² is sodium, R³ istetrahydrothiopyran-3-yl, R⁴ and R⁵ are hydrogen, Alk is CH₂ CH(CH₃) andR⁶ is p-fluorophenoxy or p-chlorophenoxy.
 14. A crop protection solidactive compound formulation as defined in claim 6, comprising glyphosateor a salt thereof as further crop protection active compound.
 15. A cropprotection solid active compound formulation as defined in claim 7,comprising glyphosate or a salt thereof as further crop protectionactive compound.
 16. A compound as in claim 13, which is the sodium saltof2-[1-(2-p-chlorophenoxypropyloxy)iminobutyl]-5-(tetrahydrothiopyran-3-yl)-3-hydroxycyclohexenone.